Complex metal compoijnds of azo



Patented Apr. 2, 1940 COMPLEX METAL COMPOUNDS F AZO ,mzns'rur'rs Max Schmid, Riehen, Switzerland, assignor to the firm Society of Chemical Industry in Basle,

Basel, Switzerland No'Draw'ing. Original application November 2,

1936, Serial No. 108,902. Divided and this application'February .4, 1938, Serial No. 188,805. In Switzerland November 6, 1935 12 Claims.

or a heterocyclic ring such as (#:hydrogen or any snbstltuent) and the like, and R1 is the residueof an organic acid, and condensing in known manner, after saponifying the radical of the organic acid, it this produce a pyrazolone capable of being coupled.

The new compounds, which correspond with the general formula in whlch a: has the meaningascribed to it above, R1 stands for hydrogen or a radical of an organic acid and Py represents the pyrazolone radical, can be converted into. new azo-dyestuffs either by coupling them with diazo-compounds or by saponifying any radical of an organic acid that may be present, then diazotizing and coupling with coupling components or by using both reactions together.

- is present, with a suitable keto compound to v The new azo-dyestufis are characterized by the presence of the atom grouping in which Py and a: have the meaning ascribed to them above and in which at least one azo-group is attached either to the pyrazolone radical or to the benzene nucleus which is not directly bound to the pyrazolone nucleus. They are particularly suitable for dyeing textiles consisting of or containing native or regenerated cellulose. The fastness. of the dyeing may in many cases be improved by after-treatment with agentsyielding metals, whereby metal complexes are formed on the fiber. Such metal complexes may be produced also in'thedye-bath, in substance, or during the formation of dyestuff;

As parent substances for compounds'of the general formula there may be mentioned benzidine, diphenyline of the formula y tolidine, dianisidine, diphenetidine, thioaniline, 4 :4 -diamino-diphenyl ether, 4 4' -diaminostilbene, 4:4'-diaminodibenzyls, 4:4'- or 323'-diaminodiphenylmethane, 4:4-diaminodiphenylamines, 4:4'- or 4:3'- or 3:l'- or 3:3'-diaminobenzoylaniline, 4:4'-diaminodiphenyl urea, the

which the linkage a: can be formulated for example as H-I' H I I l; N or (l; 1 01' ll: N H 41\ N \c% f% C I H 1\ H Compounds of the general formula are therefore, for example, monoformylbenzidine, monoacetylbenzidine, monobenzoylbenzidine, 4- or 3-acetylaminol-(4'- or 3'-amino) -benzoylaminobenzene, 4-amino-1-(4- or 3'-acetylamino) -benzoylaminobenzene-B-sulfonic acid, products obtained by monobenzoylation or monoacetylation from the reduced condensation products from 1 mol urea chloride or isocyanate from paraor meta-nitraniline and 1 mol 1:4-diaminobenzene-3-sulfonic acid, such as H o H SOaH OCH: the ternary condensation products from 1 mol 1:4- or 1:3- diaminobenzene-3- or -4=-sulfonic acid, 1 mol monoacetyl-paraor meta-phenylenediamine and 1 mol of a primary or secondary amine and 1 mol cyanuric chloride such as Such pyrazolones are, for example, the following:

( soon =N COOH OHFO/H Y,

000132 (l3 BOaH i r-E g CH =N H N H N '-C CHr-C I' l I i 1 1 t) &3 CH;

and so on, as indicated in the fifth paragraph of this specification.

Among the diazo-compounds which may be coupled with such products there must first be named the simple diazo-compounds, such as diazobenzene, diazonaphthalene, diazotoluene, diazoanisole, diazophenetole, diazotized aminoazobenzene or the like and sulfonic acids of them. Of particular interest are, however, the diazocompounds which have in orthoor peri-position to the diazo-group a hydroxyl group or a carboxyl group. Such diazo-compounds are, for example, those of ortho-aminophenols, orthoarninonaphthols and their sulfonic acids, the dimecompounds of 1:8-aminonaphthol sulfonic acids, also of ortho-aminocarboxylic acids, for instance anthranilic acid. With the aid of such compounds dyestuffs are obtained which can be converted into valuable metal compounds on the fiber or in substance by means of agents which yield metal, for instance copper salts, chromium salts or hydroxides of these metals.

Of these dyestuffs those are of especial value which are obtained by treating with copper on the fiber or in substance the azo-dyestufis which are themselves obtained by coupling the intermediate product of the. general formula with a diazotized ortho-amino-carboxylic acid of the benzene series, These new dyestuffs are therefore the copper compounds of dyestuffs of the general formula in which R2 stands for an aromatic nucleus of the benzene series which carries a COOH-group in ortho-position to the -N=N- group.

Among the coupling components which may also be coupled with the diazotized compounds of the general formula aromas in which 1 the: pyrazol'o'ne' radical may be" already coupled with a diazo+compounfd which'Ri stands for hydrogemthelteima be named compounds like phenolanaphthols, aminonaphthols and their sulfonic acids and acidyl derivatives. Specific products are, for example, para-cresol, resorcinol, s-naphthol andits sulfonicacids, the sulfonic acids of a-naphthol which couple in 2- position, aminonaphthol sulfonic acids such as Z-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-arnino-8 hydrOXynaphthaIenesulfonic acid, 1-ainino-'8-hydroxynaphthalene;4 56 d 1 s u 1 f on i 0 acid, 1-amino-8-hydroxynaphthalene-3 G-disulfonic acid (acid or alkaline coupling), 2:3-hydroxynaphthoic acid," I-acidyIamino-8-hydroXynaphthalenel su'lfonic acid, amines such as meta-phenylenediamin'e;p naphthylamine, alkyl B-naphthylamine and their sulfonic acids, azo dyestufis capable of coupling, and the like.

The dyestuffs obtained by the invention may, as already stated, especially be used for dyeing vegetable fibers. .They may also be used with a like result for dyeing regenerated cellulose, for

instance, viscose ,or copper silk. Should the-new dyestuffs containfsuitable substituents they may be diazotized o'nlth'efiber"and developed by further coupling components .orjby treatment with a. diam-compound. When the dyestuffs have b'e'en made with the aid ofjortho aminophenols, ortho aminocarboxylic acids or their esters or ethers', orwh'en they" contain-the salicylic acid grouping or other lake-forming groups of atoms they are capable of conversion into metal compounds. Suitable metals coming into question besides the copper and chromium already mentioned'are nickel, cobalt, iron, zinc or the like.

the fiber or in substance. 1 W

The new azo-dyestufis obtainable according to the present pro ess correspond to the general formula The metal-compoundsmay beobtained either on in which Ri stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, :1; standsfor a member of the group consisting of H, methyl,

phenyl, CQOH and COO* alkyl, a;v stands for a member of the group of linkages consisting of a of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms,,not more than 2 nitrogen atoms standing adjacent to each other, which ring further congroup ,doesinotbelong to the heterocyclic radical;

and astands for'a member of a'group-oi substitu ents linked to the benzene nucleusby N-- atoms and consisting of a member of the group consisting of N=N-R1, R1 standing foran aromatic nucleus from the group consisting of aromatic nuclei of the benzene and naphthalene series, and

R2 standingv for the radical of an organic acid, which dyestuffs are yellow to brown and black powders dissolving in water to yellow to orange, to brown to blackish and to green solutions, and dyeing the fiber similar tints of good fastness. The following examples illustrate. the invention, the parts being by weight: 7

Example 1 22.6 parts of finely ground monoacetyl-benzi= dine are. stirred in 50 parts of water andsome ice with 30 parts of hydrochloric acid of specific gravity 1.15. Into this mixture there is dropped slowly at 0-10 C. a solution of 7 parts of sodium nitrite in about 20 parts of water and when the addition of this nitrite is complete the whole is stirred for about'l hour and then filtered.

The filtered diazo-solution is run at 0-5 C. while stirring well into an externally cooled mixtureof partsof stannous chloridev of about 63 'per cent. strength and 50 parts of hydrochloric acid of specific gravity 1.15.

The hydrazine thus formed is sparingly soluble. After stirring for about 12 hours the mixture is filtered and the solid matter washed with dilute hydrochloric acid and then with water. By stirring this solid matter, if desired after sep- *aration of the tin, with dilute alkali the free hydrazine of the formula 1 NHf-NHOONHLGQCH;

is obtained From alcohol it crystallizes in the form of bright yellow needles'of melting point 227 0. Alternatively the filtered diazo-solution is run whilst stirring into 'amixture of 632 parts ,or bisulfite liquor of'40 per cent. strength, 30

parts of sodium'carbonate and 50 parts ofcaus'- tic soda solution of 36 B. Stirring is continued during the night and the product is salted/out and filtered. yThe filter cake is stirredinto 2000 parts of water and after addition of 60 parts of acetic acid the whole isheated to boiling. There are, then added gradually about 60 parts of. zinc dust and boiling is continued until the mass is decolorized. ,Afterfiltering hot the hydrazine sulfonic acid of the formula is salted out from the cool filtrate. r 1

The hydrazine sulfonic acid can be converted into the hydrochloride of thehydrazine .base by treatment with hydrochloric acid. In like manner products can be prepared from ,the parent materials indicated in the 5th paragraph of thisxspecification.

l j Example 2 p The hydrazine hydrochloride of the formula obtainable as described. in para rap 1+3, of,

Example 1 is boiled together with 500 parts of water and 100 parts of hydrochloric acid of specific gravity of 1.15 for about 2-3 hours, whereby the hydrochloride is dissolved. If desired the solution may be treated with sulfurated hydrogen to remove tin, if necessary, filtered and cooled. The large part of the hydrochloride separates and a further quantity may be salted out from the mother liquor or the latter may be treated with alkali to recover the free base.

This base may be recrystallized from alcohol when it forms white crystals of melting point 179 C. which become brown on exposure to air and correspond with the formula The corresponding product from mono-acetylortho, ortho'-tolidine crystallizes from alcohol in white laminae of melting point 184 C. It has the formula NME NH. on, CH2

Example 3 24.1 parts of the hydrazine of Example 1 are dissolved in about 200 parts of alcohol mixed with some glacial acetic acid. There are then added 14 parts of ethylaceto-acetate and the mixture is boiled for about 1 hour. After cooling there are added to the mixture 20 parts of caustic soda solution of 36 Be. and the mixture is stirred-for 24 hours. By heating the larger part of the alcohol is expelled while water is substituted, the whole.

is filtered and pyrazolone precipitatedby adding acid. It corresponds with the formula v The condensation may also start from the hydrazine hydrochloride and be conducted in aqueous medium. In similar manner products are obtained from the other hydrazines indicated in Example 1. Instead of ethylaceto-acetate any other fi-keto-carboxylic acid ester, for instance" ethyl benzoyl acetate, terephthaloyl di-acetic ester, ethyl 'oxal-acetate or the sodium com-' pounds thereof may be used.

Example 4 the pyrazolone precipitated by neutralization. it corresponds with the formula This new product is a white powder of melting point 194 C., soluble in dilute caustic soda solution and dilutemineral acid.

HaC-C 3 Example 5 26.5 parts of l-phenyl-(4'-phenyl-4"-amino)- 3-methyl-5-pyrazolone of the formula is salted out and separated as usual.

When dry it is a brown powder yielding yellow dyeings on cotton which may be converted into orange to red tints by diazotization on the fiber and developing, for instance with 1-phenyl-3- methyl-S-pyrazolone or fl-naphthol; the tints are fast to washing.

If diazotizing components have been used which contain OH,- OCH: or COOH in ortho-position to the diazo-group, similar products may be obtained by introducing radicals of organic acids into the amino group in 4-position and if necessary metallizing the dyestuffs.

By application of this example numerous other monoand polyazo-dyestufis capable of developement on the fiber may be produced, including dyestuffs in which the amino-group of the diphenyl-radical is diazotized in substance and coupled with such coupling components as yield dyestuffs capable of themselves being further diazotized on the fiber'and developed.

Example 6 The dyestuif obtainable by coupling 26.5 parts of l-phenyl- (4-phenyl-4"-amino) -3-methyl-5- pyrazolone with the diazo-compound from 20.7 parts of 2-chloro-l-aminobenzene--sulfonic acid in a medium alkaline with sodium carbonate is dissolved in dilute caustic soda solution and the solution is mixed with '7 parts of sodium nitrite and diazotization produced by pouring the mixture into dilute cold hydrochloric acid.

The separated diazo-compound of the dyestufi acid is filtered and the'filter cake is coupled in acetic acid medium with ammo-anyway:

naphthalene-G-sulfonic acid. -Whencoupling is componentsleadingto 'azo-dyestuii's capable of complete the dyestufl of the formula of such dyestuffs are illustrated in the following example.

Example? Thediazo-compound of the dyestuif from di-. azotized ortho-chloro-suli'anilic acid and, l-phene yl- (fif-phenyl-4' '-amino) -3-methyl-5 pyrjazolone obtainable as described in paragraph 1. of Ex-' being metallized; and coupling the diazotized and if necessary, already coppered or metallized pyrazolone azo-dyestufi with such azo-dyestuffs capable of couplingwhich have themselves been' obtained by coupling 1 mol of a diazotized diazo compound, such as aniline, sulfanilic acid, an-

thranilic acid, ortho-aminophenol-sulfonic acid,

sulfo-anthranilic acid, naphthionic acid or 1- amino 2 hydroxynaphthalene-4-sulfonic acid with 1 mol of a compound of the group consisting of resorcin. meta-phenylenediamine, metatoluylenediamine, meta-aminophenol, naphthoresorcin, cresorcinol and the like. Those dyestufis are then particularly valuable which are also metallized'in the secondpart of the molecule, already metallized dyestuffs can then also be used as coupling components. Thus the copper, cobalt, nickel and iron compounds; of the dyestuffs of the formula 1 ample 6 is coupled in a medium alkaline with sodium carbonate with the monoazo-dyestuff obtainable by acid coupling of diazotized 2:4-dichloraniline and 1-amino-8-hydroxynaphthalene- 3:6-disulfonic acid.

When dry, the isolated dyestufi of the formula is a'greenish black powder which dissolves: water to a green solution and dyes cotton pu1 e strong green tints. .7 g g Further products dyeing green may be obtained corresponding 3-carboxylic acid or the benzidine radical for tolidine, dichlorobenzidine or the like. Also the yellow pyrazolone constituent and the blue-amino-naphthol constituent of the trisazodyestuii" may be varied within widelimits. By

such changes there are obtained not only green dyestuffs, but also dyestuifs which yield quite different tints. If for example in the pyrazolone constituent the ortho-chloro-sulfanilic acid is replaced by diazotlzed aminoazo-benzene-sulfonic acid, products are obtained which dyeolive and coupled with 37,4 parts of the copper comtints., Brown dyestufis whichare very. fast to light are further obtained when using in-.the.

if the B methylpyrazolone is exchanged for the yield on cotton brown tints.

A dyestufi dyeing blackish tints is the azodyestuff which is obtained by coupling in an acid medium the diazotized cupriferous dyestufi from diazotized ortho-aminophenol sulfonic acid and l-phenyl- (4'-phenyl-4' -amino) -3-methyl-5-pyrazolone with 1-amino-8-#hydroxynaphthalene- 4:6-disulfonic acid, and further coupling the disazo-dyestufi thus obtainable with diazo-benzene in an alkaline medium.

The following data serve as example of a further dyestuff of this group:

26.5 parts of 1-pheny1-(4'-phenyl4' -amin0)-,

3-methyl-5-pyrazolone of Example 4 are dissolved in about 500 parts of water containing 10 parts of caustic soda solution of 36 B. and 15 parts of. sodium carbonate. .To the filtered solution'isadded the diazo-compound of 32 parts of dehydrothio para toluidine mono-sulfonic acid.v When coupling is complete the dyestuff is salted out and isolated.

This aminoazo-dyestuff is further diazotized pound of the azo-dyestuff from diazotized l-oxy- 2-aminobenzene-4-sulfonic acid and resorcinol.

When coupling is complete the cupriferous disazo-dyestufi formed of the probable formula 72, The complex ,copper compound of the sulfonated asymmetrical azo-dyestuffs contain- S H u on o N=NOC\ 1 l N CH: 11$ Cu I on Hols is isolated. ing at least two azo-groups of the general formula When dry it is a dark brown to black powder which dissolves in water to a brown solution and dyes cotton brown fast tints. The chromium, cobalt, nickel and iron compounds of this dyestufi also yield on cotton brown tints.

What I claim is:

1. The complex metal compounds of the sulfonated asymmetrical azo-dyestuffs containing at least two azo-groups of the general formula III (I) :N

Ill I IOH and a heterocyclic six-membered ring consisting of at least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at least twice and not more than three times the atom grouping l -NC wherein the group does not belong to the heterocyclic radical, and 2 stands for the group consisting of -N=N-R1(N=N--R2)n, n standing for zero and 1 and R1 and R2 standing for aromatic nuclei from the group consisting of aromatic nuclei of the benzene and naphthalene series, which dyestufis are soluble in water with formation of yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness.

in which R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series which is substituted in ortho-position to the --N==N, group by a substituent selected from the group consisting of 0H and COOH, 1/ stands for a member of the group consisting of H, methyl, phenyl, COOH and COO-- alkyl, or stands for a member of the group of linkagesconsisting of a diphenyl linkage, CH=CH--, -CH2-CHz-, -NH--,

and a heterocyclic six-membered ring consisting of at, least 3 and not exceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogen atoms standing adjacent to each other, which ring further contains at least twice and not more than three times the atom grouping -NC/ l N wherein the group does not belong to the heterocyclic radical,

and 2 stands for the group consisting of 50 in which y stands for a member of the group consisting of H, methyl, phenyl, COOH and COO- alkyl, R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series which is substituted in ortho-position to the --N=N- group by a'substituent selected from the group consisting of OH and coon, R15 and-Ra stand for aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series and 1?. stands for zero and 1,

' which dyestuffs are soluble in water with formation of yellow to orange, to-brown, to blackish in which 1 stands for a .memberof the group consisting of H, methyl, phenyl, COOH and C00- alkyl, R stands for a nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series which is substituted in ortho-position to the N=N group by a substituent selected from thegroup consisting of OH and COOH, R1 and R; stand for aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series and n stands for zero and 1', which dyestuffs are soluble in water with formation of yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness.

5. The complex metal compounds of the sulionated asymmetrical azo-dyestuffs containing at least two azo-groups of the general formula /N N=N"R1N=N-R: R-N=N('J-("3 n n o I in which y stands for a member of the group consisting of H, methyl, phenyl, COOH and COO alkyl, R stands for a nucleus of the benzene series substituted in ortho-position to the -N=N group by a substituent selected from the group consisting of OH and COOH groups,

andRl and R2 stand for aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, which dyestufis are soluble in water with formation of yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness.

6. The complex copper compounds of the sulfonated asymmetrical azo-dyestufis containing at least two azo-groups of the general formula in which y stands for a member of the group consisting of H, methyl, phenyl, COOH and COO- alkyl, R stands for a nucleus of the benzene series substituted in ortho-position to the --N=N- group by a substituent selected from the group consisting of OH and COOH groups, and R1 and R2 stands for aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene'series, which dyestuifs are soluble in water with formation of yellow to fastness. r

7. The complex metal compound of the sulfonated asymmetrical azo-dyestufls containing at least two azo-groups of the general formula in which R stands for a nucleus of theibenzene series substituted I in ortho-position to the -N=N group by, a substituent selected from the group consisting of OH and COOH groups, R1 and. R2 stand for aromatic nuclei selected from the group consisting, of aromatic nuclei of the benzene and naphthalene series, which dyestuffs are soluble in water with formation of yellowto'orange, 'to brown, to blackish and to green solutions, anddyeing the fiber similar tints of goodflfastness."

8. The complex copper compoundsofthe sulfonated asymmetrical azo-dyestuffs containing at least two azo-groups of the general formula in which Rstands for a nucleus of the benzene series substituted in ortho-position to the N=N-- group by a substituent selected from the group consisting of OH and COOH groups, and R1 and R: stand for aromatic nuclei selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, which dyestuffs are soluble in water with formation of yellow to orange, to brown, to blackish and to green solutions, and dyeing the fiber similar tints of good fastness.

9. The complex metal compounds of sulfonated asymmetrical azo-dyestufis containing at least two azo-groups of the general formula in which R stands for a nucleus of the benzene series substituted in ortho-position to the -N=N group by a substituent selected from the groupconsisting of OH and COOH groups, R1 stands for a nucleus of the benzene series and R2 stands for a nucleus of the benzene series substituted in ortho-position to the -N=N-- group by a OH group, which dyestuffs are soluble in water with formation of brown solutions, and dyeing the fiber brown tints of good fastness. J

10. The complex copper compounds of sulfonated asymmetrical azo-dyestufis containing at least two azo-groups of the general formula orange, to i b'rown;-2toblackish an'd'to green solu-' tions, and dyeing thefiber similar'tints of good" s 03H om C=N coon N=N-----CII(HJ n o ble in water with formation of brown solutions,

and dyeing the fiber brown tints of good fastness.

'11. The complex metal compounds of the dyestuffs of the formula in which the diphenyl radical does not contain a. substituent, which dyestuffs are soluble in water with formation of brown solutions, and dye cotton brown tints of good fastness.

12. The complex copper compound of the dyestuff of the formula in which the diphenyl radical does not contain a substituent, which dyestufi is soluble in water with formation of a brown solution, and dyes cotton brown tints of good fastness.

MAX SCHMID.

OH 803B 

